TWI378077B - Novel precursor for preparation of lithium composite transition metal oxide - Google Patents

Description

I378077 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel precursor for the preparation of a chain-complexed transition metal oxide. In particular, the present invention relates to a transition metal precursor 5 which is useful in the preparation of lithium transition metal oxides and which comprises a specific complex transition metal compound. [Prior Art] With the development of technology and the demand for mobile devices, secondary batteries have rapidly developed as a technology for 10 energy supply. Compared with other products, lithium secondary batteries have high energy density and voltage, long cycle life, And the advantages of a low self-discharge rate' are commercially available and are therefore widely used. As a cathode active material for a lithium secondary battery, lithium-containing cobalt oxide (LiCo〇2) is generally used. In addition, wUMn〇2 (having a layered crystal structure of 15) and LiMn2〇4 (having The crystal structure of the spinel contains manganese oxide and lithium nickel oxide (LiNi〇2). Among the above cathode active materials, Lic(R) 2 is a widely used material because of its preferred properties (e.g., preferred J-coating characteristics), however, it is a resource of low purity, cobalt-based raw materials. Limited and expensive, or its similar disadvantages. For example, UMN〇ALiMn2〇4, etc., is a kind of environmentally friendly material, so it is gradually replaced by LiCg02 as a cathode active material. However, Zhong Meng oxide faces disadvantages such as low capacity and cyclical noise. 4 ^78077 Therefore, a lithium/nickel-based oxide such as LiNi〇2 is not expensive relative to the cobalt-based oxide, and has a high discharge capacity when charged to 4.25 V. The reversible capacity of the doped LiNi〇2 is about 2 〇〇 mAh/g, which exceeds the capacity of LiC0〇2 (about 153 mAh/g). Therefore, regardless of the low average discharge voltage and bulk density of UNi〇2, a battery commercially containing UNi〇2 as a cathode active material can have a better energy density. Therefore, many intensive studies have focused on the application of this nickel-based cathode active material to high-capacity batteries. However, LiNi〇2_ based cathode active materials still have some problems that are not completely solved, such as high production cost 'expansion of the gas expansion caused by gas release during battery production, lower chemical stability' high pH value And similar situations. Many prior art techniques have focused on improving the properties of LiNi〇2_based cathode active materials and improving the production steps of LiNi〇2. For example, in the clock transition metal composite oxide, a part of the nickel is substituted by another transition metal element (e.g., 'Co, Μη, etc.). 15 A lithium transition metal active material containing two or more of Ni, Co, and Μη cannot be synthesized by a simple solid state reaction. Conventional > In the technique, a transition metal precursor prepared by coprecipitation or the like is used as a precursor for preparing a lithium transition metal active material. Such transition metal precursors are used in the preparation of lithium transition metal oxides, wherein the lithium transition metal oxides are optimized by controlling the particle size, or by rounding or otherwise. To achieve the desired performance by reducing the tap density. 5 1378077 Regardless of the various purposes described above, there is a long felt need in the art to develop a lithium transition metal oxide having better properties and a transition metal precursor for preparing the lithium transition metal oxide. 5 SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above problems and other technically unsolved problems. In order to solve the above problems, the inventors of the present invention have undergone various extensive and intensive research and experiments, and finally developed a novel precursor, the 10 series of which contains a composite transition metal compound, and the oxidation number of the composite transition metal compound The oxidation number of the transition metal similar to that of the lithium transition metal composite oxide is used, and when the lithium transition metal composite oxide is produced by using the former, the secondary battery can be excellent in performance. The present invention has been completed based on the above findings. According to one aspect of the invention, the above and other objects are provided. The transition metal precursor of the composite transition metal compound of the following formula 1 is used to achieve 'the transition metal precursor is used in the preparation of a lithium transition metal composite oxide (an electrode active material for a lithium secondary battery) Transition metal precursor: !0 M(〇H1.x)2 (1) where lanthanide is selected from: Ni, c〇, Mn, Babu Cu, E, ^, B, Cr, and s-periodic periodic table One or more of the group of transition metals of the second period; and 〇<χ<〇.5. 1378077 That is, the transition metal precursor of the present invention contains a novel composite transition metal compound, and the oxidation number of the transition metal of the composite transition metal compound is compared with the oxidation number of the transition metal of the lithium transition metal composite oxide. The system is greater than +2, and the oxidation number of the transition metal is preferably close to +3. 5 When a lithium transition metal composite oxide is produced using this transition metal precursor, the oxidation or reduction step for changing the oxidation number can be simplified, thereby improving process efficiency. Further, the lithium transition metal complex oxide thus obtained can have excellent performance not only as a cathode active material, but also can greatly reduce the reaction formation of by-products such as LhCO3 or LiOH.H2. The by-products of -1〇 Li2C〇3 and LiOH.f^O cause solution problems such as gelation of the slurry, lowering of the high-temperature performance of the produced battery, and high-temperature expansion. • The transition metal ruthenium drive used to prepare the lithium transition metal composite oxide (using the coprecipitation method) can be made of materials such as m(〇h) 2 and 'MOOH known in the prior art. 15 Since the oxidation number of the transition metal (M) of M(0H)2 is +2, the above problem still exists. The oxidation number of the transition metal (M) of MOOH is +3, which is the same material. The oxidation number of the transition metal oxide of the lithium transition metal composite oxide is therefore an ideal material. However, MOOH is difficult to synthesize. The synthesis of the lithium transition metal composite oxide 20 steps will be described in more detail below. For example, 'When a composite transition metal hydroxide having the form of m(〇H) 2 (m = c〇, Ni, Μη) is used as a preparation of a transition metal complex oxide containing C 〇, Ni, and ν ηη In the case of flooding, the transition metal oxidation number in the composite transition metal hydroxide is +2. When the lithium transition metal composite oxide is prepared by using the above composite transition metal hydrogen 7 1378077 oxide, the average oxidation number of the composite transition metal in the lithium transition metal composite oxide (LiM02) is +3, so it is necessary to change by the oxidation step. Oxidation number. However, when a lithium transition metal composite oxide is to be mass-produced, its oxidizing environment is not easily controlled in a high-temperature furnace due to the presence of waste gas or the like. Further, the precursor which is not oxidized becomes a by-product of the reaction and thus has a negative influence on the electrode active material. At the same time, due to the structural characteristics of each transition metal composition and its stability in aqueous solution, it is difficult to produce a transition metal oxidation number of + from a composite transition metal hydroxide containing Co, Ni, and Μη 10 . 3 and a composite transition metal hydroxide in the form of MOOH (M = Co, Ni, Μη). In particular, in the respective synthesis steps of preparing each of the hydroxides of Co, Ni, and Μη, it is impossible to separately produce a transition metal having a oxidation number of +2 and having a sin (0, 2, (: 〇 (0) , 1^11(0^)2 (space group: ?-3111) 15 form, and having a transition metal oxidation number of +3 and having Co(OOH) (space group: R-3m, P63/mmc) and Mn ( OOH) (space group: PBNM, P121/C1, PNMA, PNNM, B121/D1) metal hydroxide. However, a single form of MOOH having two or more of Co, Ni, and Μ is synthesized. The phase is very difficult. It is difficult to synthesize a composite precursor under the same conditions (coprecipitation conditions) because of the precipitation conditions between Co, Ni, and ΜN and the atomic structure. Problem, the inventors of the present invention conducted various extensive and intensive experiments. Finally, a novel composite transition 1378077 metal compound was invented, and the oxidation number of the transition metal was similar to that of the lithium transition gold eyebrow composite oxide. That is, the successful development of the inventor of the present invention Compared with M(OH)2 with an oxidation state of +2, M(OH)2 has a higher transition metal oxidation state of 5^(ΟΗ^χ)2'. This is a non-MOOH (oxidation state is +3, but in practical application) A novel compound which is difficult to synthesize, which can be produced in large quantities and exhibits high efficiency when synthesized by a transition metal composite oxide. Here, the oxidation number of the composite transition metal compound is similar to lithium. The oxidation number of the transition metal of the transition metal composite oxide means that the oxidation number of the transition metal of the composite-10 transition metal compound is less than or close to that of the lithium transition metal composite oxide (produced by a precursor containing the above compound) The oxidation number of the transition metal. Therefore, when the oxidation number of the transition metal of the lithium transition metal composite oxide (such as the mark 式 in the formula LiM〇2) is +3, the transition metal oxide of the composite transition metal oxide The number can be, for example, greater than +2 and less than 15 +3. Within the measurement error range, even if the transition metal oxide number of the composite transition metal compound is +3, it means that the composite transition metal compound is at least one The crystal structure is different from the material of the conventional crystal structure. For example, as the experimental junction in Experimental Example 2 to be described later, the composite transition gold 20 compound of the present invention has an absorption peak different from that of MOOH and M(OH). The measurement result of the crystal structure in the conventional technique of 2), which means that even when the value of X in the composite transition metal oxide is very close to 〇5 or even when the value of X is measured within the error range, At 5 o'clock, the composite transition metal oxide of the present invention has a crystal structure different from the conventional one. 9 1378077 In a preferred embodiment, the value of cerium may be 0 2 $ χ < 0.5, more preferably 〇 · 3 $χ<0,5. In Formula 1, the oxime is composed of an element selected from two or more of the elements defined above. In a preferred embodiment, the lanthanide contains a transition metal selected from one or more of the group consisting of Ni, c〇, and Μη, so that at least one of the transition metals can be deduced. It can be expressed in lithium transition metal composite oxides. In particular, the ruthenium may preferably comprise two transition metals selected from the group consisting of Ni' Co, & ,η, or all of the transition metals included therein. In a preferred embodiment The compound in which niobium contains Ni, Co, and/or Μη can be made of a composite transition metal compound represented by Formula 2:

NibMricCowc+oMYOUz (2) 15 where 0.3^^0.9, O.lScSO.6, OSdSO.l, b+c+dg and 0 <x<0.5 'and Μ' are selected from A, Mg, Cr, Ti, A group of Si, and any combination thereof. That is, the composite transition metal compound of Formula 1 may be a composite transition metal compound containing Ni, Co, and Μη as shown in Formula 2, and a part of Ni, 20 Co, and Μη is selected from A. Substituting one or more elements of the group of Mg, Cr, Ti, and Si. The composite transition metal compound has a high Ni content, and thus is preferably used for the production of a cathode active material for a high-capacity lithium secondary battery. 1378077 The transition metal precursor of the present invention contains at least a composite transition metal as shown in the formula Compound. In a preferred embodiment, the transition metal precursor may comprise a composite transition metal compound in an amount of 3% by weight or more, preferably 50% by weight or more. The remaining material constituting the precursor of the present invention may be modified except for the composite transition metal compound, and includes, for example, a composite transition metal hydroxide having an oxidation number of +2. As the examples and experimental examples which will be described below, the transition metal I precursors can be fabricated on a lithium transition metal composite oxide having excellent characteristics as compared with the transition metal precursors which do not contain the complex transition metal compound of Formula 1. -10 in. Further, the present invention provides a composite transition metal compound of the formula, which is a novel material as described above with respect to the prior art. In the process of making the clock transition metal composite oxide, the use of the transition metal precursor containing the composite transition metal compound can simplify the oxidation or reduction step for changing the oxidation number, and thus is used for controlling the oxidation or reduction environment. The steps will be very simple and convenient. Further, in contrast to the case where such a composite transition metal compound is not used, the thus obtained ruthenium metal complex telluride exhibits an excellent effect b as a cathode active material. Moreover, in the process of producing a transition metal oxide, the produced by-products (such as Li2C〇3, LiOH, H2〇, etc.) are significantly reduced, so that the problems caused by some by-products during the production of the battery can be solved ( Such as gelation of mud, reduced efficiency under high temperature operation of the battery, high temperature expansion, and the like. The preparation of the transition metal precursor of the present invention will be described in detail below. 1378077 Transition metal precursors can be prepared using a transition metal-containing salt and a base material using a coprecipitation method. The co-intensification method is a method of precipitating two or more transition metal elements together in an aqueous solution via a sinking reaction. Specifically, a package of 5 composite transition metal compounds containing two or more transition metals can be prepared by mixing a transition metal-containing salt at a predetermined molar ratio in accordance with the transition metal content to produce a Aqueous solution. And adding a strong base (such as sodium hydroxide or the like), then adding an additive (such as ammonia source or the like) to the aqueous solution t as needed, and then maintaining the pH of the solution in an alkaline state to 10 targets The product coprecipitated. By appropriately controlling the temperature, pH, reaction time, concentration of the slurry, ion concentration, and the like, the average particle diameter = particle diameter distribution and particle density should be appropriately controlled. reaction? The value of 11 may be between 9 and 13, preferably between 10 and 12. More suitably, the reaction can be carried out in a multi-stage manner. The salt of the 15 + transition metal preferably has an anion and is easily decomposed and volatilized in the sintering step, and thus may be a sulfate or a light salt. Examples of sulfates or nitrates may include, but are not limited to, sulfuric acid, acid drill, sulfuric acid chain, nickel nitrate, cobalt nitrate, and nitric acid. Base materials may include, but are not limited to, sodium hydroxide, gas oxidizing, 20, and lithium hydroxide. It is preferably sodium hydroxide. In a preferred embodiment, an additive and/or carbonic acid test which forms a complex with the transition metal may be added to the coprecipitation step. Examples of the additives which can be used in the present invention include an ammonia ion source, an ethylenediamine compound, an acid compound, and the like. Examples of the gas ion source may include ammonia water, butyl sulfide 12 1378077 aqueous ammonium acid solution, aqueous ammonium nitrate solution, and the like. The carbonate base may be selected from the group consisting of ammonium carbonate, sodium carbonate, potassium carbonate, and lithium carbonate. These materials may be used singly or in combination with each other. The amount of the additive or the carbonate used can be appropriately determined depending on the amount of the transition metal-containing salt, the pH, and other conditions. According to the reaction conditions, and following the following examples, a transition metal precursor containing only the composite transition metal compound of Formula 1 may be prepared, or a transition metal precursor containing other complex transition metal compounds may be prepared. come out. According to another aspect of the present invention, a lithium transition metal composite oxide prepared from the above transition metal precursor is provided. In particular, a lithium transition metal composite oxide which can be used as a cathode active material for a lithium secondary battery can be prepared by a transition metal precursor oxide and a clock transition metal composite oxide prepared by sintering a material containing the via material. It is used for electrode active materials through secondary batteries. The transition metal composite oxide can be used alone or in combination with a conventional electrode active material for a lithium secondary battery. It has been confirmed by the inventors of the present invention that a by-product (e.g., a carbonic acid 20 chain (Li2C〇3) or a hydrogenated chain (LiOH)) is used in the chain transition metal composite oxide obtained by using the above-mentioned transition metal precursor. The content is very low. Therefore, when this transition metal composite oxide is used as an electrode active material of a chain secondary battery, there are many advantages including ultra-high temperature stability (such as excellent sintering and storage stability) and reduction of gas release), high capacity. And superior cycle characteristics. 13 1378077 The lithium-containing metal material is not particularly limited and may include, for example, lithium hydroxide, lithium carbonate, and lithium oxide. Preferably, it is lithium carbonate (LhCO3) or lithium oxychloride (LiOH). Further, the lithium transition metal oxide may be a compound containing two or more transition metals. Examples of the transition metal oxide may include, but are not limited to, a layered compound (e.g., an oxidized diamond (LiCo〇2) substituted with one or more transition metals and an oxidized chain (LiNi〇2)); a transition oxide substituted by one or more transition metals; such as the formula LiNh.yMyC^ (M = Co, Μη, A1, Cu' Fe, Mg, B, Cr, Zn, Ga, or any combination thereof, and 〇10 The listed oxides; and

Lii+zNibMncC〇i.(b+c+d)MdO(2-e)Ne (-0.5<z<0.5 '〇.3<b<0.9 ' O.lScSOJ, OSdSO.l, 0SeS0.05 and b +c+d<l; Μ = A, Mg, Cr, Ti, Si or Y; and N = F, P or Cl), a chain of nickel-cobalt composite oxides such as Li1+zNi1/3Co1/3Mn1/ 302 and Li1+zNi04Mn〇.4Co〇.2〇2. In particular, the 'chain transition metal composite oxide may preferably be a chain transition metal composite oxide containing c〇, Ni, and Μη. The reaction conditions for preparing a lithium transition metal composite oxide by reacting a transition metal precursor with a lithium-containing material have been conventionally used, and therefore are not described herein. Further, the present invention provides a lithium transition metal composite oxide comprising the above lithium transition metal composite oxide. A cathode as a cathode active material, and a lithium secondary battery containing the cathode. For example, the cathode can be produced by applying a cathode active material of the present invention, a conductive material, and a binder to a cathode/8077 pole current collector, followed by drying. In addition, the mixture is added to the above mixture as needed. Can add a more

Ίο 15

20 The cathode current collectors are generally manufactured to have a thickness of 3 to 500 Å. The material of the cathode current collector is not particularly limited as long as it has high conductivity and: causes chemical changes in the battery fabricated therewith. Examples of the material of the cathode current collector may be: stainless steel, sinter, nickel, chin, sintered carbon, and (4) stainless steel having a surface treated with carbon, nickel, & or silver. The resulting cathode current collector can have a fine surface which can enhance the adhesion to the cathode active material. In addition, the current collectors can have a variety of styles including: film, sheet, foil, mesh, void structure 'foam, and non-woven fibers. The conductive material is generally added in an amount of from 1 to 20% by weight based on the total weight of the mixture of the cathode active materials of the package 3. The conductive material is not particularly limited as long as it has appropriate conductivity and does not cause chemical changes in the battery fabricated therefrom. Examples of the conductive material may include: graphite, such as natural graphite, or artificial graphite; Carbon black, such as carbon black, acetylene ink, Ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers, such as carbon fibers, and metal fibers; metal powders, such as carbon fluoride, private chains, and powders, conductive whiskers, such as oxidation and potassium acid; conductive metal oxides, such as titanium oxide; A phenyl derivative (polyphenylene) derivative. The binder is a composition for assisting the bonding between the electrode active material and the conductive material, and the bond between the electrode active material and the current collector 15 1378077. The binder is generally added in an amount of from 1 to 20% by weight based on the total mass of the mixture containing the cathode active material. The material of the binder can be: polyvinylidene fluoride, polyvinyl alcohols, carboxymethylcellulose (CMC), 5 starch, propylcellulose. (hydroxypropylcellulose), regenerated cellulose, and polyethylene. Polyvinyl pyrollidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM)), sulfonated EPDM, styrene butadiene rubber, fluoro rubber, and various copolymers. A filler can be selectively used and used to suppress expansion of the cathode. The filler is not particularly limited as long as it does not cause a chemical change in the battery fabricated therefrom and is a fibrous material. Examples of fillers 15 may include: olefin polymers such as polyethylene and polypropylene; and fibrous materials such as glass fibers and carbon fibers. A lithium secondary battery generally includes a cathode, an anode 'a separator, and a non-aqueous electrolyte containing a lithium salt. The other components contained in the lithium secondary battery of the present invention are described in detail below. 20 The anode was prepared by applying an anode material to an anode current collector followed by drying. The composition described below may be further included as needed. Examples of the anode material of the present invention may include: carbon such as non-graphitic carbon, and graphite-based carbon; metal composite oxides such as LixFe203 (OSxSl), LixW02 (0 such as 1), and SnxMet-xMe'yOz (Me: Μη) , Fe, Pb or Ge; 16 1378077

Me' : Ab B, P, Si, the first element of the periodic table, the element of the „family and the ΠΙ family, or the dentate; (χα; (5) illusion; and ^$8); lithium metal; lithium alloy ; bismuth based alloy; tin based alloy; metal oxides, such as Sn 〇, Sn 〇 2

Pb〇, Pb〇2, Pb2o3, Pb3o4, Sb203, Sb204, Sb2〇5, Ge0, 5 Ge〇2, Bi2〇3, Bi2〇4, and Bi2〇5; conductive polymers such as polyacetylene; and Li- Co-Ni based material. 10 15 20 The anode current collector is generally 3 to 5 inches thick. The material of the anode anode current collector is not particularly limited as long as it has suitable conductivity and does not cause chemical changes in the battery fabricated therefrom. Just fine. Examples of the material of the anode current collector may be copper, copper, or carbon, or aluminum or cadmium alloy treated with carbon, nickel, titanium, or silver. Like the cathode current collector, the anode current collector may also be in the form of a fine irregular shape on the surface to enhance adhesion to the anode active material. In addition, the anode current collector can have a money pattern including: a film, a sheet, a sheet, a mesh, a pore structure, a foamed shape, and a non-woven fabric. The separator is disposed between the cathode and the anode. As the separator, a separator having high ion permeability and mechanical strength can be used. The separator has a pore diameter of 0.01 to 10//111 and a thickness of 5 to 3 Torr. As the separator, 'a sheet-like or non-woven fabric made of an olefin polymer (e.g., polypropylene, and/or glass fiber, or polyethylene) which is chemically resistant and hydrophobic can be used. When a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte can be used as both a separator and an electrolyte. 17 1378077 Lithium-containing non-aqueous electrolyte consists of a non-aqueous electrolyte and lithium. As the nonaqueous electrolyte, a nonaqueous electrolyte solution, an organic solid electrolyte, or an inorganic solid electrolyte can be used. Examples of the non-aqueous electrolyte solution used in the present invention may include: 5 an aprotic organic solvent such as N-methyl-2-pyrollidinone, propylene carbonate, ethylene carbonate Ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyro 10 lactone, 1 1,2-dimethoxy ethane, tetrahydroxy Franc, 2-methyltetrahydro 0-French (2-methyl 16 & 117 (11'〇) £1^311), 曱基基亚石风(<1111161;11丫15111[〇\1<^), 1,3-dioxinol (1,3-dioxolane), formamide , dimethyl form amide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate ), phosphoric acid triester, trimethoxy methane, dioxin derivative Dioxolane derivatives), sulfolane, methyl sulfolane, 1,3-dimercapto-2-° m. Cyclohexanone 2 〇 (l,3-dimethyl-2-imidazolidinone ), propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, ethyl propionate, And the like. 1378077 Examples of the organic solid electrolyte used in the present invention may include: a polyethylene derivative, a poly(ethylene oxide) derivative, a poly(oxypropylene) derivative, a vinegar-filled polymer, and a poly search. Poly agitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and a polymer containing a 5-part dissociative group. Examples of the inorganic solid electrolyte used in the present invention may include: nitrides, halides, and sulfates such as Li3N, Lil, Li5NI2,

Li3N-LiI-LiOH, LiSi04, LiSi04-LiI-LiOH, Li2SiS3, Li4Si04, _Li4Si〇4-LiI-LiOH, and Li3P〇4-Li2S-SiS2. • 10 Lithium salt is a material that is easily soluble in non-aqueous electrolytes, and may include, for example, Lie, LiBr, Lil, LiC104, LiBF4, LiB10Cl10, LiPF6, LiCF3S03, LiCF3C02, LiAsF6, LiSbF6, LiAlCU, CH3S03Li, CF3S03Li, (CF3S02) 2NLi, chloroborane lithium, lower aliphatic 15 carboxylic acid lithium, lithium tetraphenyl borate, and imide . In addition, in order to improve charge/discharge characteristics and flame retardancy, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, and B may be used. Ethylene 20 (n-glyme), hexaphosphoric triamide, nitrobenzene derivatives, sulfur, and terephthalic acid Amine dye (quinone imine. dyes), N-substituted N-substituted oxazolidinone, N,N-substituted 0,0-N-substituted imidazolidine, ethylene glycol 1378077 Ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-meth〇Xy ethan〇l, aluminum trichloride, Or an analog thereof is added to the non-aqueous electrolyte. [Embodiment] Hereinafter, embodiments of the present invention will be described by way of specific embodiments. The details of the present invention can be variously modified and changed without departing from the spirit and scope of the invention. The embodiment is merely an example for convenience of explanation. [Example 1] A 3 L wet reaction tank was filled with 2 l of saturated water and nitrogen gas was continuously supplied at a rate of 1 L/min to remove dissolved oxygen in the water. The temperature of the distilled water in the tank was maintained at 45 to 50 〇c ^ using a thermostat, and the distilled water was stirred at a rate of 1000 to 1200 rpm using a pusher provided outside the tank 15 and connected to the motor. 20 A nickel sulfate, cobalt sulfate, and manganese sulfate were mixed at a molar ratio of 0.55:0.2:0.25 to prepare a 15M aqueous transition metal solution. In addition, a 3 M aqueous sodium hydroxide solution was also prepared. Then, the aqueous solution of the transition metal is continuously driven into the wet reaction tank at a rate of 〇L/hr by a metering pump, and the sodium hydroxide aqueous solution is driven into the reaction tank by a control unit to adjust the reaction tank. The pH value of the water in the wet water tank keeps the pH value of the steamed water in the wet reaction tank from the oldest to the oldest. The aqueous ammonia solution is continuously fed into the reaction tank at a rate of O.OWO.ML/h as an additive. . 20 1378077 The flow rates of the aqueous transition metal solution, aqueous sodium hydroxide solution, and aqueous ammonia solution must be adjusted so that the average residence time of the solution in the wet reaction tank is maintained at 5 to 6 hours. When the reaction in the tank is stable, it is continued for a period of time to synthesize a composite transition metal precursor having a higher density. 5 When reaching a steady state, the nickel-cobalt-manganese composite transition metal precursor (the transition metal ion in the transition metal aqueous solution, the hydroxide ion of sodium hydroxide, and the ammonia ion of the aqueous ammonia solution are continuously continuous for 2 hours) The reaction is formed by flowing out through the overflow tube on the top end of a tank. > The obtained composite transition metal precursor was washed several times with distilled water, and dried by a constant temperature oven at 120 ° C for 24 hours to obtain a nickel-cobalt-manganese composite transition metal precursor. [Example 2] A transition metal precursor was prepared in the same manner as in Example 1 except that the temperature in the wet reaction tank was maintained to be outside 45 °C. 15 [Example 3] A transition metal precursor was prepared in the same manner as in Example 1 except that the rate at which the aqueous ammonia solution was added to the wet reaction tank was adjusted to 〇 03 > to 0-035 L/hr. [Example 4] 20 A transition metal was prepared in the same manner as in Example 1 except that the concentration of the aqueous solution containing nickel sulfate, cobalt sulfate, and sulfuric acid was changed to 2 M, and the concentration of the aqueous sodium hydroxide solution was changed to 4 M. Precursor. [Example 5] 21 1378077 The rate of addition of the aqueous ammonia solution to the wet reaction tank was adjusted to 0.03.

The transition metal precursor was prepared in the same manner as in Example 1 to 0.035 L/hr' and the internal temperature of the wet reaction tank was maintained at 4 to 45 °C. [Example 6] 5 A transition metal was prepared in the same manner as in Example 1 except that the pump was adjusted to the condition of shifting so that the pH of the saturated water in the wet reaction tank was maintained at 10.5 to 11 Torr. Precursor. [Example 7] The internal temperature of the wet reaction tank was maintained at 4 to 45. 〇, and 10 need to adjust the pump to the condition of shifting to maintain the pH of the steamed water in the wet reaction tank at 1 〇, 5 to 11.0, and prepare the transition metal precursor in the same manner as in Example 1. . [Comparative Example 1] A 3 L wet reaction tank was filled with 2 [distilled water and nitrogen gas was continuously supplied at a rate of i L/min 15 to remove dissolved oxygen in the water. Use a thermostat to maintain the temperature of the saturated water in the tank at 45 to 5 ° C ^ and use a pusher that is placed outside the tank and connected to the motor at 1 to 12 rpm. The rate is stirred with distilled water. Sulfuric acid, cobalt sulfate, and manganese sulfate were mixed at a molar ratio of 20 〇·55:0.2:0.25 to prepare a 2.0 M aqueous transition metal solution. In addition, a 4 M aqueous sodium hydroxide solution was also prepared. Next, a metering pump was used to continuously pump the transition metal aqueous solution at 0.18 L/hr into the wet reaction tank. The sodium hydroxide aqueous solution is driven at a variable speed by a control unit to adjust the pH of the steamed water in the reaction tank to steam in the wet reaction tank 22 1378077 5

Part Np X y Z atom Occ. Beq. Ni 1 0 0 0 Ni 0.55 1.73 (6) Co 0.2 The pH of the distilled water is maintained between 10.0 and 10.5. A 30% aqueous ammonia solution was continuously fed as an additive to the reaction vessel at a rate of 〇.〇1 to 0.015 L/hr to obtain a composite transition metal precursor. [Experimental Example 1] The nickel-cobalt-manganese composite transition metal precursor obtained in Example 1 was subjected to a neutron diffraction experiment. The neutron diffraction experiment was performed at room temperature using the HANARO HRPD instrument, the 32 He-3 Multi-detector system, and the Ge (331) monochromatic light (the experimental location is located in South Korea). , Korea Atomic Energy Research Institute (KAERI). The data was collected at an angle of 2 Θ = 10 and 150 ° at Δ (2 0 ) = 0.05 ° and at a light wavelength of 1.8334 A for 3 hours. The sample size is between 10 and 15 g. The TOPAS program was used to combine the X-ray and neutron diffraction data and perform Rietveld correction (correction parameters: scale factor, background value, unit cell parameter, atomic coordinates, thermal parameters, occupancy of H1). The results obtained are shown in Figure 1 and Table 1. <Table 1> Sample Ref [(Ni0.55Co0.2Mn0 25)(OH0 53)2] Space group P-3m a(A) 3.0350(2) c(A) 4.5523(7) Crystal size 41.5(5) ( Nm)__ 23 1378077 Μη 0.25 0 2 0.33333 0.66667 0.2122(8) 0 1 Η * ϋ·妹d 2 b ruin 0.33333 0.66667 lord 4® 0.396(3) Η 0.526(6) *The numerical value of the numerical value in parentheses represents the standard variation The number of plants 2 is about 3 (5. As shown in Fig. 1 and Table 1, the nickel-cobalt-manganese composite transition metal precursor system obtained in Example 1 is MCOH^)2, which is unknown in the prior art. 5 structure. [Experimental Example 2] The X-ray diffraction experiment was carried out by taking the drill-and-burst composite transition metal precursors of Examples 1 to 7 and Comparative Example 1, respectively. The number of X-ray diffraction experiments is 15Υ2Θ^75. , with △ (2Θ) = 0.025. 1〇 2 hours at room temperature, using a copper target and a Lynxeye detector

The Bragg-Brentano diffractometer (Bruker-AXS D4 Endeavor) collects. The X-ray and neutron diffraction data are combined and Rietveld corrected using the T0PAS program (correction parameters: scale factor, background value, unit cell number 15, atomic coordinates, thermal parameters, occupancy of H1). The results obtained are shown in Figures 2 and 3 and Table 2, respectively. 2 is a χ-light diffraction peak of the nickel-cobalt-manganese composite transition metal precursor of Example 1 and a conventional precursor M (〇H) 2 and M〇〇H having a conventional theoretical crystal structure. Diffraction peaks. Table 2 below shows the analysis results of the parent-light diffraction peak of Fig. 3. 20 <Table 2> Sample (101) (001) (101) / (001) (101), (1〇1) / [(1〇1) + (101),] 24 1378077 Example 1 16671 24248 0.69 - 100% Example 2 10734 31336 0.34 3116 77.5% Example 3 10802 31960 0.34 2456 81% Example 4 43990 99076 0.44 15735 74% Example 5 20383 51299 0.40 6204 77% Example 6 10501 31895 0.33 2653 79% Example 7 46791 99410 0.47 48316 50% Comparative Example 1 (001), 51506 (101)7(001), 0.84 43290 0 (101)',(001)': m(oh)2 (101), (001): M( OH, .x) 2 I * Both materials have an overlap in the (001) equatorial intensity ratio (except Comparative Example 1). 5 First, as shown in Fig. 2, the nickel-cobalt-manganese composite transition metal precursor obtained in Example 1 has a novel structure which is not known in the prior art. In particular, the transition metal precursor of Example 1 has a structure different from that of the conventional transition metal precursor M(0H)2, and is also different from the structure of 1^〇〇11. Close to 0.5 and within the specific range of the present invention, or the actual value of 10 x is 0.5 within the measurement error range, that is, even when the value of the transition metal oxidation number of the composite ruthenium transition metal ruthenium drive is +3 In the case of the present invention, the drill-and-burst composite transition metal precursor is a new material different from Μ00Η. As shown in FIG. 3 and Table 2, the embodiment 1 has only the wave 15 of Μ(〇Ηΐχ)2. Peaks, while Examples 2 through 7 have an integrated intensity ratio, or a ratio above this peak. From these results, it can be seen that the nickel-cobalt-manganese composite transition metal precursor of Example 1 contains only M(〇HUx)2, whereas the nickel, cobalt-manganese composite transition metal precursors of Examples 2 to 7 coexist with M. (〇H| A is 25 1378077 and M(OH) 2 » In addition, it can be seen that the nickel-cobalt-manganese composite transition metal precursor of Comparative Example 1 contains only m(oh) 2. Further by the method of Example 1 The position of the peak and the peak position of M(〇h) 2 are based on relatively different results. The expression of the precursor of Example 6 can be corrected to 5 by MKOHbxh, where χ$〇.35. [Examples 8 to 14 and comparison Example 2] The nickel-cobalt-manganese composite transition metal ruthenium extracts obtained in Examples 1 to 7 and Comparative Example 1 were individually mixed with LifO3 at a ratio of 1:1 (w/w). The film was heated at a rate of ° C /min and sintered at 92 ° C for 1 hour 10 to prepare a Li[NiQ 55Co〇.2Mn()_25]〇2 cathode active material powder. The cathode active material powder and conductive material were prepared ( Denka black), and a binder (KF1100) were mixed at a ratio of 95:2.5: 2, 5 to prepare a slurry which was applied to an aluminum (A1) foil having a thickness of 2 Å. The aluminum foil coated with the slurry was dried at 130 ° C to prepare a lithium secondary battery. 15 The lithium secondary battery cathode, lithium metal foil (as a counter electrode (anode)), polyethylene film (obtained as described above) was used. Celgard, thickness: 20 / / m, as a separator), and 1M LiPFe solution (as a liquid electrolyte) to make a 2 〇 16 coin-shaped battery 'LiPFe solution is dissolved in ethylene carbonate, dimethylene carbonate A solution of a mixture of dimethylene carbonate and diethyl carbonate mixed in a ratio of m 20 [Experimental Example 3] An electrochemical analysis system (Toyo System, Toscat 3100U) was used in a voltage range of 3.0 to 4.25 V. The characteristics of the cathode active materials in the coin-shaped batteries produced in Examples 8 to 4 and Comparative Example 25 were tested. 26 1378077 The results are shown in Table 3 below. &lt;Table 3&gt; Sample Charging (mAh/g) Discharge (mAh/g) Efficiency (%) Example 8 (Example 1) 188 Ϊ67.1 88.9 Food Example 9 (Example 2) 185.5 163.4 87.1 Example 10 (Example 3) 186.1 163.4 87.8 Greedy Example 11 (Example 4) 184.3 160 86.8 ΪΓExample 2184 160.1 87 Example 13 (Example 6) 181.1 156.1 86.2 Example 14 (Example 7) (Example 5) 180.4 85.9 155 Comparative Example 2 (Comparative Example 1) 79.4 178.7 141.9

As a result of the results shown in Table 3, the chain secondary batteries of Examples 8 to 14 contained 5 lithium transition metal composite oxides (as cathode active materials) produced using the transition metal precursor of the present invention, as compared with the comparative examples. The secondary battery obtained by using the m(OH)2 precursor has better performance even under the same composition. [Experimental Example 4] 1 Li The value of the Li by-product value in the transition metal composite oxides of Examples 8 to 14 and Comparative Example 2 was measured by pH titration. Specifically, 10 g of each lithium transition metal composite oxide was mixed with 1 〇〇 mL of distilled water for 5 minutes, and the lithium transition metal complex oxygen 27 1378077 was removed by filtration. The residual solution was titrated with a 0 1 N HCl solution to determine the value of its lithium by-product. The end point of the titration was pH 5. The results are as described in Table 4 below. <Table 4> Sample initial pH 0.1 N HC1 (mL) Li by-product (wt%) Example 8 (Example 1) 10.9 4.8 0.115 Example 9 (Example 2) 11.1 5.8 0.138 Example 10 (Example 3) 11.2 5.3 0.127 Example 11 (Example 4) 11.4 6.7 0.161 Example 12 (Example 5) 11.4 6.1 0.148 Example 13 (Example 6) 11.5 7.4 0.172 Example 14 (Example 7) 11.5 7.8 0.181 Comparative Example 2 (Comparative Example 1) 11.8 11.5 0.256 From the results of Table 4, it is understood that the transition metal of the present invention is used as compared with the lithium transition metal composite oxide of Comparative Example 2 obtained by using the M(〇H) 2 precursor. The lithium transition metal composite oxide (Examples 8 to 14) prepared by the precursor has a significant decrease in the by-product stem. Further, it is also known that as the by-product of the clock 10 decreases, ΐνΚΟΗ,.χ) The content of 2 is significantly increased. The above-described embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited by the scope of the claims. Industrial Applicability 28 1378077 In summary, the transition metal oxidation number of the novel transition metal precursor for preparing a lithium transition metal composite oxide of the present invention approximates the transition metal oxidation number in the lithium transition metal composite oxide. Therefore, when a lithium transition metal composite oxide is produced using a precursor, the oxygenation or reduction step for changing the oxidation number can be simplified, thereby improving process efficiency. In addition, the lithium transition metal composite oxide thus obtained can have excellent performance not only as a cathode active material, but also can greatly reduce by-products such as Li2C03 or

The reaction of LiOH*H2〇) is generated. The reaction product of Li2C03 and Li0H.H20 may cause solution problems, such as gelation of mud, lowering of efficiency when the battery is operated at high temperature, and high temperature expansion. [Simplified illustration] Fig. 1 is the experimental example 1. Test the resulting graph. 2 is an analysis result of the X-ray diffraction peak of the nickel-cobalt-manganese composite transition metal precursor of Example 1 in Experimental Example 2, and a conventional crystal structure having a theoretical crystal structure. ) Comparison of the diffraction peak results of 2α & ΜΟΟΗ materials. Fig. 3 is a comparison result of the χ_light diffraction bee obtained in Experimental Example 2. [Main component symbol description] 20 None. 29

Claims (1)

1378077 VII. Patent application scope: 1. A transition metal precursor used as a transition metal precursor for preparing a lithium transition metal composite oxide, the transition metal precursor system comprising a composite transition metal as shown in Formula 1. Compound: 5 Μ(〇Η,.χ)2 (1) where: lanthanide is selected from: Ni, Co, Μη, Al, Cu, Fe, Mg, Β, Cr, and the transition of the second cycle of the periodic table Two or more groups of metals; and 10 〇 &lt;x&lt;0.5. 2. The transition metal precursor according to claim 1, wherein the oxidation number of the oxime in the formula 1 is similar to the oxidation number of one of the transition metal of the lithium transition metal composite oxide. 3. The transition metal precursor according to claim 2, wherein the oxidation number of the enthalpy in the formula 1 is approximately +3. 4. The transition metal precursor according to claim 1, wherein the X value in the formula 1 is 〇.2$χ&lt;〇.5. 5. The transition metal precursor according to claim 1, wherein the X value in the formula 1 is 0_3$χ&lt;0.5. 20 6 ^ 中 ° ° The transition metal precursor described in claim 1 contains one or more transition metals selected from: Ni, Co, and 》 30 1378077 5 .10 15 The transition metal precursor according to claim 6, wherein the lanthanide comprises two or a transition metal selected from the group consisting of: Ni, Co, and Μη. 8. The transition metal precursor according to claim 1, wherein the composite transition metal compound is a composite transition metal compound as shown in Formula 2: NibMncC〇i.(b+c+d)M, d(〇H,.x)2 (2) where: 〇.3&lt;b&lt;0.9;0.1&lt;c&lt;0.6;0&lt;d&lt;0.1;b+c+d&lt;l;0&lt;x&lt;0.5; M is selected from the group consisting of: AI, Mg, Cr, Ti, Si, and any combination thereof. 9. The transition metal precursor according to claim 1, wherein the composite transition metal compound is contained in an amount of 30% by weight or more based on the total weight of the transition metal precursor. 10. The transition metal precursor according to claim 9, wherein the composite transition metal compound is contained in an amount of 50% by weight or more based on the total weight of the transition metal precursor. 11. A composite transition metal compound, as shown by the formula: m(〇H,.x)2 (1) wherein Μ and X are as defined in the scope of the patent application. 31 1378077 12-Lithium transition metal composite oxide prepared by using the transition metal precursor as described in claim 1 of the patent application. A lithium secondary battery comprising the lithium transition metal composite oxide as described in claim 2, as a cathode active material. 32